BR102015010657A2 - mercaptosilanes containing urea, the process for its preparation and its uses - Google Patents

Abstract

Urea-containing mercaptosilanes, process for their preparation and their uses. The present invention relates to urea-containing mercaptosilanes of formula I (i) which is prepared by reacting a halosilane of formula ii (ii) with the compounds of formula iii (iii) in an alcohol.

Description

Report of the Invention Patent for "MER-CAPTOSSILANS CONTAINING UREA, PROCESS FOR THE PREPARATION FOR THEIR USES". The present invention relates to urea-containing mercaptosilanes, processes for their preparation and their use. CAS 1082204-82-7, 1268617-33-9 and 104261-54-3 disclose compounds of formula. In addition, JP 2008279736 A discloses urea-containing silanes for coatings. DE 3424534 A1 discloses N, N'- and N, '', Ν '-substituted urea-containing silanes of the formula [005] The preparation is carried out by the reaction of a -minine compound, a halosilane and a metal cyanate alkaline in an aprotic polar organic solvent, for example DMF or DMSO. In addition, JP 2002311574 discloses powder coatings comprising the silanes of the formula R1-S-R2-NH-C- (0) -NH-R3-Si (R4) m (0R5) 3.m [007] WO 9955754 A1 describes photosensitive resin compositions comprising alkoxysilanes of the formula [(R10) 3-a (R2) aSi-R3-AC (0) -B] mX. The disadvantages of known urea-containing mercaptosilanes are poor processing characteristics, low net density, poor wet slip properties and low dynamic stiffness. It is an object of the present invention to provide urea-containing mercaptosilanes having improved processing characteristics, lattice density, wetting properties and dynamic stiffness in rubber mixtures compared to the urea-containing mercaptosilanes known in the prior art.

The invention provides a urea-containing mercaptosilane of formula I wherein R1 are the same or different and are C1-C10 alkoxy groups, preferably methoxy or ethoxy group, C2-C10 cyclic dialoxy groups, phenoxy group, cycloalkoxy groups C4-C10, C6-C20 aryl groups, preferably phenyl, C1-C10 alkyl groups, preferably methyl or ethyl, C2-C20 alkenyl group, C7-C20 aralkyl or halogen group, preferably Cl, R2 is a group of monovalent C1-C20 hydrocarbon, preferably a C1-C20 alkyl group, C6-C20 aryl group, C2-C20 alkenyl group or C7-C20 aralkyl, and R are the same or different and are a branched or unbranched group, saturated or unsaturated, aliphatic, aromatic or mixed divalent aliphatic / aromatic C1-C30, preferably C1-C20, more preferably C1-C10, even more preferably C1-C7, especially preferably C2 and C3, a hydrocarbon group optionally substituted by F-, Cl-, Br-, I-, -CN or HS -. The urea-containing mercaptosilanes may be mixtures of the urea-containing mercaptosilanes of formula I. The process product may comprise oligomers formed by hydrolysis and condensation of alkoxysilane functions of the urea-containing mercaptosilanes of formula I. Urea-containing mercaptosilanes of formula I may be applied to a support, for example, wax, polymer or carbon black. Urea-containing mercaptosilanes of formula I may be applied to silica, in which case the bond may be physical or chemical. R may preferably be -ch2-, -ch2ch2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH (CH3) -, -CH2CH (CH3) -, -CH (CH3) CH2-, -C (CH3) 2-, -CH (C2H5) -, -CH2CH2CH (CH3) -, -CH (CH3) CH2CH2-, -CH2CH (CH3) CH2-, -ch2ch2ch2ch2ch2-, -ch2ch2ch2ch2ch2ch2-, -ch2ch2ch2ch2ch2ch2ch2ch, -ch2ch2ch2ch2ch2ch2ch2ch2ch ch2ch2ch2ch2ch2ch2ch2ch2ch2-, -ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2-, -ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2-, -ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2-, -ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2-, -ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2 CH2- or [0016] R1 may be preferably methoxy or ethoxy. R2 may preferably be CH3, CH2CH3, CH2CH2CH3 or (CH2) 6CH3. The urea-containing mercaptosilanes of formula I may preferably be: (CH3CH2O) 3Si-CH2-NH-O-NH-CH2-SC (O) -CH3, (CH3CH20) 3Si-CH2CH2-NH-CO-NH-CH2 -SC (0) -CH3, (CH3CH20) 3Si-CH2-NH-C0-NH-CH2CH2-SC (0) -CH3i (CH3CH20) 3Si-CH2CH2-NH-C0-NH-CH2CH2-S <:( 0) -CH3i (CH3CH20) 3Si-CH2CH2CH2-NH-C0-NH-CH2-SC (0) -CH2 (CH3CH20) 3Si-CH2CH2CH2-NH-CH2CH2-SC (0) -CH3, (CH3CH20) 3Si -CH2-NH-C0-NH-CH2CH2CH2-SC (0) -CH3, (CH3CH20) 3Si-CH2CH2-NH-CH2CH2CH2-SC (0) -CH3, (CH3CH20) 3Si-CH2CH2CH2-NH-C0 -NH-CH2CH2CH2-SC (0) -CH3, (CH3CH20) 3Si-CH2-NH-C0-NH-CH2-SC (0HCH2) 6CH3, (CH3CH20) 3Si-CH2CH2-NH-C0-NH-CH2-SC ( (CH3CH2) 6CH3, (CH3CH20) 3Si-CH2-NH-C0-NH-CH2CH2-S <:( 0MCH2) 6CH3i (CH3CH20) 3Si-CH2CH2-NH-CH2CH2-S4 (0) - (CH2) 6CH3, (CH3CH20) 3Si-CH2CH2CH2-NH-CO-NH-CH2-SC (0) - (CH2) 6CH3, (CH3CH20) 3Si-CH2CH2CH2-NH-CH2CH2-SC (0) - (CH2) 6CH3, (CH3CH20) 3Si-CH2-NH-C0 -NH-CH2CH2CH2-SC (0) - (CH2) 6CH3, (CH3CH2O) 3Si-CH2CH2-NH-CO-NH2CH2CH2CH2-SC (O) - (CH2) 60H3, (CH3CH20) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2CH2-SC (0) - ( CH2) 6CH3, (CH30) 3Si-CH2 -NH-C0 -NH-CH2 -S-C (O) -CH3, (CH30) 3Si-CH2CH2 -NH-C0 -NH-CH2 -S-C (O) -CH3. (CH30) 3 Si-CH2 -NH-CO-NH-CH2 CH2 -S-C (O) -CH3. (CH30) 3Si-CH2CH2-NH-CO-NH-CH2CH2-SC (0) -CH3, (CH30) 3Si-CH2CH2CH2-NH-C0-NH-CH2-SC (0) -CH3, (CH30) 3Si-CH2CH2CH2 -NH-C0-NH-CH2CH2-SC (0) -CH3, (CH30) 3Si-CH2-NH-C0-NH-CH2CH2CH2-SC (0) -CH3, (CH30) 3Si-CH2CH2-NH-C0-NH -CH2CH2CH2-SC (0) -CH3, (CH30) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2CH2-SC (0) -CH3. (CH30) 3Si-CH2-NH-CO-NH-CH2-SC (0) - (CH2) 6CH3, (CH30) 3Si-CH2CH2-NH-CO-NH-CH2-SC (0) - (CH2) 6CH3 ( (0) - (CH2) 6CH3, (CH30) 3S1 -CH2-NH-C0-NH-CH2CH2-SC (0) - (CH2) 6CH3, (CH30) 3S1 -CH2CH2CH2-NH-C0-NH-CH2-SC (0) - (CH2) 6CH3, (CHaOJaSi-CHzCHzCHz-NH-CO-NH-CHzCHz-S-CyOHCHzJeCHa, (CH30) 3Si-CHz NH-C0-NH-CH2CH2CH2-SC (0) - (CH2) 6CH3, (CHsOJsSi-CHzCHz-NH-CO-NH-CHzCHzCHz-S-C HOHCHzJeCHs, (CHaOJaSi-CHzCHzCHz-NH-CO-NH-CHzCHz-S- An especially preferred compound is of the formula (EtO) * 3Si-CH 2 CH 2 CH 2 -NH-C 0 -NH-CH 2 CH 2 -SC (O) -CH 3.

The invention further provides a process for the preparation of the inventive urea-containing mercaptosilanes of formula I.

Wherein R1, R2 and R are each as defined above which is characterized by the fact that a halosilane of formula II

Being reactive with a compound of formula III wherein R1, R2 and R are each as defined above, Hal is F, Cl, Br or I, preferably Cl, and M is an alkali metal, preferably of K or Na in an alcohol. The halosilanes of formula II may preferably be: (C2H50) 3Si-CH2 -NH-C (O) -NH-CHz-CI, (CzHsO4 Si-CHzCHz-NH-C10JNH-CHz-CI, ( CzHsO4 Si-CHzCHzCHz-NH-C2 -NH-CHz-CI, (CzHsOhSi-CHz-NH-C2 -NH-CHzCHz-CI, (CzHgObSi-CHzCHz-NH-C10H NH-CHzCHz-CI, (CzHsObSi -CH 2 CH 2 CH 2 -NH-CH 2 CH 2 -NH-CH 2 CH 2 -C 1 (C 2 H 50) 3 Si-CH 2 -NH-C (O) -NH-CH 2 CH 2 CH 2 -C 2, (CzHgOJS 1 CH 2 CH 2 -NH-CH 2 CH 2 CH 2 CH 2 -C 2 (C 2 H 5 O 2 -CHzCHzCHz-NH-CIO-NH-CHzCHzCHz-CI, (CH30) 3Si-CH2-NH-C (0) -NH-CH2-CI, (CH30) 3Si-CH2CHz-NH-C (0) -NH-CHz -Cl, (CH30) 3Si-CH 2 CH 2 CH 2 -NH-C (O) -NH-CH 2 -CH (CHaOJSi-CHz-NH-C 10 H NH-CHzCHz-CI (CH 30) 3Si-CH 2 CH 2 -NH-C (0 ) -NH-CH2CH2-CI, (CH30) 3Si-CH2CH2CH2-NH-C (0) -NH-CH2CH2-CI, (CH30) 3Si-CH2-NH-C (0) -NH-CH2CH2CH2-CI, (CH30) ) 3Si-CH 2 CH 2 -NH-C (O) -NH-CH 2 CH 2 CH 2 -C 1 or (CH 30) 3Si-CH 2 CH 2 CH 2 -NH-C (O) -NH-CH 2 CH 2 CH 2 -C 1 The compounds of formula III may preferably be: NaS-C (0) -CH3, NaS-C (0) -CH2CH3, NaS-C (0) -CH2CH2CH3, NaS-C (0) - (CH2) 6CH3, KS-C (0) -CH3, KS- C (0) -CH2CH3i KS-C (0) -CH2CH2CH3 or KS-C (0) - (CHz) 6CH3. According to the invention, the halosilane of formula II may be measured for the compound of formula III. In the process according to the invention, the compound of formula III may preferably be measured for halosilane of formula II. In the process according to the invention, the halosilane of formula II may be used relative to the compound of formula III in a molar ratio of 0.85: 1 to 1.15: 1, preferably 0.90: 1. at 1.10: 1, more preferably in a ratio of 0.95: 1 to 1.05: 1. [0029] The reaction may be conducted excluding air. The reaction may be carried out under a protective gas atmosphere, for example under an argon or nitrogen atmosphere, preferably under nitrogen. The process of the invention may be carried out at atmospheric pressure, high pressure or reduced pressure. Preferably, the process according to the invention may be carried out under normal pressure. High pressure may be a pressure of 110 to 10000 kPa (1.1 bar to 100 bar), preferably 150 to 5000 kPa (1.5 bar to 50 bar), more preferably 200 to 2000 kPa (2 20 bar) and most preferably from 200 to 2000 kPa (2 to 10 bar). Reduced pressure may be a pressure from 0.1 to 100 kPa1 mbar to 1000 mbar, preferably from 0.1 to 50 kPa (1 mbar to 500 mbar), more preferably from 0.1 to 25 kPa (1 mbar 250 mbar), most preferably from 0.5 to 10 kPa (5 mbar to 100 mbar). (convert) The process according to the invention may be carried out between Ό 'and 150 °, preferably between 20 and 100 ° C. and 100 ° C, more preferably between δΟΌ and 80Ό. Especially preferably, the process according to the invention may be carried out at the boiling point of the alcohol. The alcohol used in the process according to the invention may preferably be methanol, ethanol, propanol, butanol or cyclohexanol. The alcohol may especially preferably be ethanol. Alcohol may preferably be removed by distillation after the reaction. The reaction product may be further dried. Drying may be carried out at temperatures of + 20 ° C + +, preferably + 25 ° C + 75 ° C. Drying can be performed at a reduced pressure of 0.1 to 50 kPa (1-500 mbar). The urea-containing mercaptosilane of formula I obtained by the process according to the invention may be obtained in a yield of greater than 50%, preferably greater than 60%, most preferably greater than 70%.

In one embodiment, halosilane of formula II, prior to reaction with the compound of formula III, may be prepared from the hydrochloride salt of an amine of formula IV.

It is an isocyanatosilane of formula V by the addition of a base, preferably NaOEt, wherein Hal, R 1 and R are each as defined above. The base may be added until a pH value between 7 and 14 is established. In the process according to the invention, the hydrochloride salt of an amine of formula IV may be used in relation to the isocyanatosilane of formula V, in a molar ratio of 0.85: 1 to 1.15: 1, preferably 0 90: 1 to 1.10: 1, more preferably in a ratio of 0.95: 1 to 1.05: 1.

In the above-mentioned embodiment, the process according to the invention for the preparation of urea-containing mercaptosilanes of formula I

Where R1, R2 and R are each as defined above, may be characterized in that the amine hydrochloride salt of formula IV is dissolved in alcohol and reacted with the base, then the isocyanatosilane of formula V

[0049] is added, and then the compounds of formula III are added, the mixture is filtered and the solvent is removed, wherein Hal, M, R1, R2 and R are each as defined above.

In another embodiment, halosilane of formula II, prior to reaction with the compound of formula III, may be prepared from the isocyanate-halogen compound of formula VI.

[0052] and the aminosilane of formula VII wherein Hal, R and R1 are each as defined above. The reaction may be conducted in a solvent, preferably alcohol, more preferably ethanol. In the process according to the invention, the i-socianate halogen compound of formula VI may be used relative to the α-minosilane of formula VII, in a molar ratio of 0.85: 1 to 1.15: 1, preferably 0.90: 1 to 1.10: 1, more preferably in a ratio of 0.95: 1 to 1.05: 1.

In the above-mentioned embodiment, the process according to the invention for the preparation of urea-containing mercaptosilanes of formula I

Wherein R1, R2 and R are each as defined above may be characterized by the fact that an isocyanate-halogen compound of formula VI

[0058] and the aminosilane of formula VII

Reacted in alcohol, preferably ethanol, and then a compound of formula III is added, the mixture is filtered and the alcohol is removed, where Hal, M, R, R 1 and R 2 are each as defined above. . The product prepared by the process according to the invention may have a residual halosilane content of formula II of less than 25 mol%, preferably less than 10 mol%, more preferably less than 5 mol%, very high. preferably less than 3 mol%. The relative molar percentages of halosilane of formula II in the product prepared by the process according to the invention are determined in the 1 H NMR by integrating the hydrogen atoms of the -CH2CH2-CI group of halosilane of formula II against the hydrogen atoms of urea-containing mercaptosilane group Si-CH2- of formula I. In the case of the substance of formula II (EtO) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2-CI, for example, the integral of the hydrogen atoms of the group -CH2CH2-CI (δ = 3.17 ppm) is used for the determination of relative contents. The product prepared by the process according to the invention may have a residual hydrochloride salt content of an amine of formula IV of less than 25 mol%, preferably less than 10 mol%, more preferably less than 5%. mol, most preferably less than 3 mol%. The relative molar percentages of the hydrochloride salt of an amine of formula IV in the product prepared by the process according to the invention are determined in 13 C NMR by the integration of the carbon atoms in the group -CH2-NH2-HCl of the hydrochloride salt of an amine of formula IV against the carbon atoms in the Si-ÇH2- group of the urea-containing mercaptosilane of formula I. In the case of the substance of formula IV ΗΟΙ · Η2Ν-ΟΗ2-ΟΗ2-ΟΙ, for example, the integral of the carbon atoms of the HCl group H2N-CH2-CH2-CI (δ = 41.25 ppm) or HCl-H2N-CH2-CH2-CI group (δ = 40.79 ppm) is used for the determination of relative levels. The product prepared by the process according to the invention may have a residual isocyanatosilane content of formula V of less than 10 mol%, preferably less than 5 mol%, more preferably less than 1 mol%, very high. preferably less than 0.1 mol%. The relative molar percentages of the isocyanatosilane of formula V in the product within a range of> 1 mol%, prepared by the process according to the invention, are determined in the 13 C NMR by the integration of the carbon atoms of the isocyanatosilane -N group of the formula V against the carbon atoms in the Si-CH2- group of the urea-containing mercaptosilanes of formula I. In the case of the substance of formula V (EtO) 3Si-CH2-CH2-CH2-NCO, for example, the integral of the carbon atoms of the group NÇO (δ = 122.22 ppm) is used for the determination of relative contents within a range of> 1 mol%. The relative molar percentages of the isocyanatosilane of formula V in the product within a range of <1 mol%, prepared by the process according to the invention, are determined by quantitative FT-IR spectroscopy known to those skilled in the art. The method is calibrated using appropriate concentration calibration solutions (eg in C2Cl4). For the measurement, about 1 g of the sample is weighed into a 25 ml long-necked bottle, and 25 g of C 2 Cl 4 is added. The sample is stirred on a shaker for 1-2 hours. Thereafter, the lower liquid phase is cautiously measured in a 20 mm IR cuvette and analyzed by FT-IR spectroscopy (4000-1200 cm -1, 2 cm -1 resolution). Under the same conditions, a solvent spectrum is recorded for subtraction. In the case of the substance of the formula V (EtO) 3 Si-CH 2 -CH 2 -CH 2 -NCO, for example, the wavelength of the valence vibration of the -NCO group at 2270 cm -1 is used for the determination relative contents within a range of <1 mol%. The product prepared by the process according to the invention may have a residual content of the isocyanate-halogen compound of formula VI of less than 25 mol%, preferably less than 10 mol%, more preferably less than 5%. mol, most preferably less than 3 mol%. The relative molar percentages of the isocyanate-halogen compound of formula VI in the product prepared by the process according to the invention are determined in the 13 C NMR by the integration of carbon atoms in the OÇN-CH2- group of the isocyanate-halogen compound of formula VI against the carbon atoms in the Si-OH2- group of the urea-containing mercaptosilane of formula I. In the case of the substance of formula VI OCN-CH2-CH2-CI, for example, the carbon atom integral of OÇN-CH2- group (δ = 124.33 ppm) is used for the determination of relative levels. The product prepared by the process according to the invention may have a residual content of aminosilane of formula VII of less than 10 mol%, preferably less than 5 mol%, more preferably less than 1 mol%, very high. preferably less than 0.1 mol%. The relative molar percentages of aminosilane of formula VII in the product prepared by the process according to the invention are determined in the 13 C NMR by the integration of carbon atoms in the group -CH2-NH2 of the aminosilane of formula VII against carbon atoms in the Si-CH2- group of the urea-containing mercaptosilane of formula I. In the case of the substance of formula VII (EtO) 3Si-CH2-CH2-CH2-NH2, for example, the integral of the carbon atoms of the group - CH2-NH2 (δ = 45.15 ppm) is used for the determination of the relative content. The urea-containing mercaptosilane of formula I prepared by the process according to the invention may be characterized by one of the method 1H, 13C or 29Si NMR known to those skilled in the art. The soluble fraction of the urea-containing mercaptosilane of formula I in the products obtained by the processes according to the invention in DMSO-d6 or CDCl3 is determined by the addition of an internal standard, for example triphenylphosphine oxide (TPPO), in DMSO -d6 or CDCl3, and a 1H NMR method known to those skilled in the art. Urea-containing mercaptosilanes of formula I may be used as adhesion promoters between inorganic materials, for example glass beads, glass shards, glass surfaces, glass fibers or preferably silica fillers such as precipitated silicas and fumed silicas, and organic polymers, for example thermosetting, thermoplastics or elastomers, or as cross-linking agents and surface modifying agents for oxidic surfaces. Urea-containing mercaptosilanes of formula I may be used as coupling reagents in rubber filler mixtures, such as tire treads, industrial rubber articles or footwear soles. The advantages of the inventive urea-containing mercaptosilanes of formula I are improved processing characteristics, mesh density, wet skid properties and dynamic stiffness in rubber blends.

Examples Comparative Example 1: Preparation of (EtO) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2-SH from (EtO) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2-CI and NaSH [0085] To a solution of NaSH in ethanol [prepared by introducing H2S (15.21 g, 0.45 mol, 1.07 eq) into a solution of sodium eoxide (prepared from Na (10.55 g 0.46 mol, 1.10 eq) in EtOH (300 mL))] is added, by the measured addition at 52Ό, (E-tO) 3Si-CH 2 CH 2 CH 2 -NH-CO-NH-CH 2 CH 2 -C (138.90). g, 0.42 mol, 1.00 eq) in ethanol (300 ml), and the mixture is heated to 780 ° C. After a reaction time of 5 h, the mixture is cooled to room temperature and the suspension is filtered. The filtrate is released from the solvent in a rotary evaporator and dried under reduced pressure. The (EtO) 3 Si-CH 2 CH 2 CH 2 -NH-CO-NH-CH 2 CH 2 -SH (134.96 g, 97.9% of theory) is obtained as a white solid. 1H-NMR (δppm, 500 MHz, CDCl3): 0.64 (2H, t), 1.23 (9H, t), 1.36 (1H, br), 1.61 (2H, m) , 2.67 (2H, t), 3.17 (2H, m), 3.37 (2H, m), 3.81 (6H, q), 4.74 (1H, br), 4.94 ( 1H, br); 13 C NMR (δ ppm, 125 MHz, CDCl 3): 7.8 (1 C), 18.3 (3 C), 23.8 (1 C), 25.6 (1 C), 43.0 (1 C) 43.5 (1C), 58.4 (3C), 158.9 (1C).

Example 1: Preparation of (EtO) 3Si-CH 2 CH 2 CH 2 -NH-CO-NH-CH 2 CH 2 -S-CO-CHs from (EtO) 3Si-CH 2 CH 2 CH 2 -NH-CO-NH-CH 2 CH 2 -C and KSAc (EtO) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2-CI (81.52 g, 0.25 mol, 1.00 eq) is initially charged in ethanol (85 ml) in a 500 ml three-necked flask with stirrer, reflux condenser and internal thermometer. Potassium thioacetate (28.48 g, 0.25 mol, 1.00 eq) is added and the mixture is heated to reflux. After a reaction time of 3.5 hours, the mixture is cooled to room temperature and the suspension is filtered. The filtrate is released from the solvent on a rotary evaporator and dried under reduced pressure. The product (E-tO) 3 Si-CH 2 CH 2 CH 2 -NH-CO-NH-CH 2 CH 2 -S-CH 3 (81.64 g, 89% of theory) is obtained as a light brown solid. 1H-NMR (δppm, 500 MHz, CDCl3): 0.64 (2H, t), 1.24 (9H, t), 1.61 (2H, m), 2.35 (3H, s) 3.01 (2H, t), 3.16 (2H, t), 3.34 (2H, t), 3.82 (6H, q), 4.5-7.0 (2H, br); 13 C NMR (δ ppm, 125 MHz, CDCl 3): 7.8 (1C), 18.3 (3C), 23.8 (1C), 29.9 (1C), 30.6 (1C), 40.0 (1C), 43.0 (1C), 58.4 (3C), 159.0 (1C), 195.8 (1C).

Example 2: Preparation of (EtO) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2-S-CO-CH3 from (EtO) 3Si-CH2CH2CH2-NH2, OCN-CH2CH2-CI and KSAC [0091] 3-Aminopropyltriethoxysilane (132.82 g, 0.60 mol, 1.00 eq) is initially charged in ethanol (300 ml) in a three-necked flask with precision glass stirrer, internal thermometer, decanting funnel and reflux condenser, and cooled to -78 °. Chloroethyl 2-isocyanate (63.34 g, 0.60 mol, 1.00 eq) is added dropwise at -78 to -68Ό within 1.75 h and then the mixture is heated to 50 ° C. *THE. Potassium thioacetate (68.53 g, 0.60 mol, 1.00 eq) is added in five portions and the mixture is heated to reflux. After a reaction time of 2.25 h, the mixture is cooled to room temperature and the suspension is filtered. The filtrate is released from the solvent on a rotary evaporator and dried under reduced pressure. The (E-tO) 3 Si-CH 2 CH 2 CH 2 -NH-CO-NH-CH 2 CH 2 -S-CH 3 product (213.91 g, 97.3% of theory) is obtained as a waxy white solid. 1H-NMR (δppm, 500 MHz, CDCl3): 0.64 (2H, t), 1.22 (9H, t), 1.62 (2H, m), 2.35 (3H, s) 3.01 (2H, t), 3.16 (2H, t), 3.34 (2H, t), 3.82 (6H, q), 4.7-5.0 (2H, br); 13 C NMR (δ ppm, 125 MHz, CDCl 3): 7.8 (1C), 18.3 (3C), 23.8 (1C), 29.9 (1C), 30.6 (1C), 40.1 (1C), 43.0 (1C), 58.4 (3C), 158.7 (1C), 195.9 (1C).

Example 3: Preparation of (EtO) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2-S-CH3 from (EtO) 3Si-CH2CH2CH2-NCO, HCl-H2N-CH2CH2-CI and KSAC [0094] 2-Chloroethylamine (73.86 g, 0.70 mol, 1.00 eq) is initially charged with ethanol (2.0 I) in a 3-neck 4-liter flask with precision glass stirrer, internal thermometer Decantation funnel and reflux condenser, and cooled to -78 °, and sodium ethoxide (226.83 g, 0.70 mol, 1.00 eq, 21% in ethanol) is added. 3-Isocyanatopropyl (triethoxysilane) (173.15 g, 0.70 mol, 1.00 eq) is then added dropwise at -78 to -65 ° within 3 h and then the mixture is heated to 50 °. Potassium thioacetate (79.95 g, 0.70 mol, 1.00 eq) is added in five portions and the mixture is heated to reflux. After a reaction time of 4 h, the mixture is cooled to room temperature and the suspension is filtered. The filtrate is released from the solvent on a rotary evaporator and dried under reduced pressure. The (EtO) 3 Si-CH 2 CH 2 CH 2 -NH-CO-NH-CH 2 CH 2 -S-CH 2 CH 3 product (288.02 g, quant.) Is obtained as an orange oil.

Example 4: Rubber Blends The formulation used for rubber blends is specified in Table 1 below. In this table, the phr unit means parts by weight based on 100 parts by weight of the raw rubber used. The inventive silane is used in isomolar amounts relative to comparative silane.

Table 1 Substances used: (a) NR TSR: SIR 20 SED, by Aneka Bumi Pratama (TSR = technically specified rubber; SIR = Indonesian standard rubber) [0097] b) BR: polybutadiene, Europrene Neocis BR 40, of C) SSBR: Sprintan® SLR-4601 from Styron [db] d) silica: ULTRASIL® VN3 GR from Evonik Industries AG [e] 6PPD: N- (1'-dimethylbutiO-rsT-phenyl -p-phenylenediamine f) DPG: diphenylguanidine 9) CBS: N-cyclohexyl-2-benzothiazolesulfenamide The mixture was produced under usual two-stage conditions in a laboratory kneader for production. rubber mixtures (volume from 300 milliliters to 3 liters), first mixing in the first mixing phase (base mixing phase) all components other than the vulcanization system (sulfur and vulcanizing influencing substances) to 145 at 16513, reaching temperatures from 152 to 15713, from 200 to 600 seconds. Addition of the vulcanization system in the second phase (ready mix phase) yields the final blend, with mixing at 90 to 12013 for 180 to 300 seconds. [00104] The general process for producing rubber and vulcanized mixtures thereof is described in "Rubber Technology Handbook", W. Hofmann, HanserVerlag 1994. [00105] Rubber testing is performed by the test methods specified in Table 2.

The mixtures were used to produce pressurized vulcanization test samples at 160 amostras after 15 t95 (measured on a mobile cavity rheometer to ISO 6502 / ASTM D5289-12). Table 3 presents the rubber data for vulcanized ones. Table 3 Rubber blend II comprising the inventive urea-containing mercaptossilane of Example 2 shows improved processing characteristics (lower minimum torque after 3rd mixing step), increased network density (larger maximum torque difference - torque). minimum), improved wet skid properties (23Ό rebound resilience) and increased dynamic stiffness (E 'at 0.15% elongation, E' at 8% elongation, and E 'at 8% elongation) E 'at 0.15% elongation) as compared to the reference rubber mixture I comprising Comparative Example 1 (urea-containing mercaptosilane) used in isomolar amounts.

Claims (13)

1. Urea-containing mercaptosilane of formula I where R1 are the same or different and are C1-C10 alkoxy groups, C2-C10 cyclic dialoxy groups, phenoxy group, C4-C10 cycloalkoxy groups, C6-C20 aryl groups, C1-alkyl groups -C10, C2 -C20 alkenyl group, C7 -C20 aralkyl or halogen group, R2 is a monovalent C1-C20 hydrocarbon group, and R are the same or different and are a branched or unbranched, saturated or branched hydrocarbon group unsaturated, aliphatic, aromatic or mixed divalent aliphatic / aromatic C1-C30. Urea-containing mercaptosilane according to Claim 1, characterized in that the urea-containing mercaptosilane is of the formula I (CH 3 CH 20) 3 Si-CH 2 -NH-C 0 -NH-CH 2 -SC (0) -CH 3, (CH 3 CH 20) 3Si-CH2CH2-NH-C0-NH-CH2-SC (0) -CH3, (CH3CH20) 3Si-CH2-NH-C0-NH-CH2CH2-SC (0) -CH3, (CH3CH20) 3Si-CH2CH2-NH- C0-NH-CH2CH2-SC (0) -CH3, (CH3CH20) 3Si-CH2CH2CH2-NH-C0-NH-CH2-SC (0) -CH3, (CH3CH20) 3Si-CH2CH2CH2-NH-C0-NH-CH2CH2- SC (0) -CH3, (CH3CH20) 3Si-CH2-NH-C0-NH-CH2CH2CH2-SC (0) -CH3, (CH3CH20) 3Si-CH2CH2-NH-C0-NH-CH2CH2CH2-SC (0) -ch3 , (CH 3 CH 20) 3 Si-CH 2 CH 2 CH 2 -NH-C 0 -NH-CH 2 CH 2 CH 2 S-c (0) -ch 3, (CH 3 CH 20) 3 Si-CH 2 -NH-C 0 -NH-CH 2 SC (0) - (CH 2) 6 CH 3, (CH3CH20) 3Si-CH2CH2-NH-C0-NH-CH2-SC (0) - (CH2) 6CH3, (CH3CH20) 3Si-CH2-NH-CH2CH2-SC (0) - (CH2) 6CH3, (CH3CH20) 3Si-CH2CH2-NH-C0-NH-CH2CH2-SC (0) - (CH2) 6CH3, (CH3CH20) 3Si-CH2CH2CH2-NH-C0-NH-CH2-SC (0) - (ch2) 6ch3, (CH3CH20) 3Si-CH2CH2CH2-NH-CO-NH-CH2CH2-SC (0) - (CH2) 6CH3, (CH3CH20) 3Si-CH2-NH-CH2CH2CH2-SC (0) - (CH2) 6CH3, (CH3CH20) 3Si-CH2CH2-NH-C0-NH-CH 2CH 2 CH 2 -S-C (0) - (CH 2) 6 CH 3 or (CH 3 CH 20) 3 Si-CH 2 CH 2 CH 2 -NH-C 2 -NH-CH 2 CH 2 CH 2 -S-C (0) - (CH 2) 6 CH 3. Urea-containing mercaptosilane according to Claim 1, characterized in that the urea-containing mercaptosilane is of the formula I (Et0) 3 Si-CH 2 CH 2 CH 2 -NH-C 0 -NH-CH 2 CH 2 -S-C (0) -CH 3. Process for the preparation of urea-containing mercaptosilane as defined in claim 1, characterized in that the halosilane of formula II is reacted with the compounds of formula III wherein R 1, R 2 and R are each as defined in claim 1, Hal. is F, C, Br or I and M is an alkali metal in an alcohol. Process for the preparation of the urea-containing mercaptosilane of formula I according to claim 4, characterized in that the reaction is conducted under a protective gas atmosphere. Process for the preparation of the urea-containing mercaptosilane of formula I according to claim 4, characterized in that the reaction is conducted at temperatures between 0 ° C and 150 ° C. Process for the preparation of the urea-containing mercaptosilane of formula I according to claim 4, characterized in that the alcohol used is ethanol. Process for the preparation of the urea-containing mercaptosilane of formula I according to claim 4, characterized in that the halosilane of formula II is prepared from the hydrochloride salt of an amine of formula IV HCl H2N'R'Hal ( (γ) and isocyanatosilane of formula V (R1) 3srR'Nco by the addition of a base, wherein Hal, R1 and R are each as defined in claim 4. Process for preparing the urea-containing mercaptosilane of formula I according to claim 8, characterized in that the base used is NaOEt. Process for the preparation of the urea-containing mercaptosilane of formula I according to claim 4, characterized in that the halosilane of formula II is prepared from the isocyanate-halogen compound of formula VI OCN R'Hal (VI) and aminosilane of formula VII (R 1) 3 sRR 1 NH 2 (VM) wherein Hal, Re R 1 are each as defined in claim 4. Process for preparing the urea-containing mercaptosilane of formula I according to claim 10, characterized in that the reaction is conducted in ethanol. Process for the preparation of the urea-containing mercaptosilane of formula I according to any one of claims 4 to 10, characterized in that the alcohol is distilled. Process for preparing the urea-containing mercaptosilane of formula I according to claim 12, characterized in that the product obtained is dried.